CN114685356A - Arylamine carbazole compound and organic electroluminescent device containing same - Google Patents

Arylamine carbazole compound and organic electroluminescent device containing same Download PDF

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CN114685356A
CN114685356A CN202011598579.8A CN202011598579A CN114685356A CN 114685356 A CN114685356 A CN 114685356A CN 202011598579 A CN202011598579 A CN 202011598579A CN 114685356 A CN114685356 A CN 114685356A
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尚书夏
王芳
吴秀芹
张兆超
李崇
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention discloses an arylamine carbazole compound and an organic electroluminescent device containing the same, belonging to the technical field of semiconductor materials, wherein the structure of the compound is shown as a general formula (1). The arylamine carbazole compound is bridged by an aromatic ring, and carbazole and arylamine are dispersedly connected on the aromatic ring, so that the arylamine carbazole compound has excellent hole transport capability, film phase stability and weather resistance. When the novel arylamine carbazole-based compound is used for forming a hole transport material of an organic electroluminescent device, the effects of improving the device performance, such as improving the device efficiency, reducing the driving voltage, prolonging the service life and the like, can be displayed.

Description

Arylamine carbazole compound and organic electroluminescent device containing same
Technical Field
The invention relates to the technical field of semiconductors, in particular to a novel arylamine carbazole compound and an organic electroluminescent device which contains the arylamine carbazole compound and is applicable to various display devices.
Background
Carriers (holes and electrons) in an organic electroluminescent device (OLED) are injected into the device from two electrodes of the device respectively under the driving of an electric field, and meet recombination to emit light in an organic light emitting layer. High performance organic electroluminescent devices require various organic functional materials to have good photoelectric properties. For example, as a charge transport material, it is required to have good carrier mobility. The hole injection layer material and the hole transport layer material used in the existing organic electroluminescent device have relatively weak injection and transport characteristics, and the hole injection and transport rate is not matched with the electron injection and transport rate, so that the composite region has large deviation, and the stability of the device is not facilitated. In addition, reasonable energy level matching between the hole injection layer material and the hole transport layer material is an important factor for improving the efficiency and the service life of the device, and therefore, how to adjust the balance between holes and electrons and adjust the recombination region is an important subject in the field.
Blue organic electroluminescent devices are always soft ribs in the development of full-color OLEDs, and the efficiency, the service life and other properties of blue light devices are difficult to be comprehensively improved at present, so that how to improve the properties of the blue light devices is still a crucial problem and challenge in the field. Most of blue host materials currently used in the market are electron-biased hosts, and therefore, in order to adjust the carrier balance of the light-emitting layer, a hole-transporting material is required to have excellent hole-transporting performance. The hole injection and transmission are better, the adjusting composite region can shift towards the side far away from the electronic barrier layer, so that the light is emitted far away from the interface, the performance of the device is improved, and the service life is prolonged. Therefore, the hole transport region material is required to have high hole injection property, high hole mobility, high electron blocking property, and high electron weatherability.
Since the hole transport material has a thick film thickness, the heat resistance and amorphousness of the material have a crucial influence on the lifetime of the device. Materials with poor heat resistance are easy to decompose in the evaporation process, pollute the evaporation cavity and damage the service life of devices; the material with poor film phase stability can crystallize in the use process of the device, and the service life of the device is reduced. Therefore, the hole transport material is required to have high film phase stability and decomposition temperature during use. However, the development of materials for stable and effective organic material layers for organic electroluminescent devices has not been sufficiently realized. Therefore, there is a continuous need to develop a new material to better meet the performance requirements of the organic electroluminescent device.
Disclosure of Invention
In order to solve the above problems, the present invention provides an arylamine carbazole-based compound and an organic electroluminescent device comprising the same. The arylamine carbazole compound is bridged by an aromatic ring, and carbazole and arylamine are dispersedly connected on the aromatic ring, so that the arylamine carbazole compound has excellent hole transport capability, film phase stability and weather resistance. When the novel arylamine carbazole-based compound is used for forming a hole transport material of an organic electroluminescent device, the effects of improving the device performance, such as improving the device efficiency, reducing the driving voltage, prolonging the service life and the like, can be displayed.
The technical scheme of the invention is as follows:
an arylamine carbazole compound has a structure shown in a general formula (1):
Figure BDA0002868384810000011
Figure BDA0002868384810000021
ar is1-Ar4Each independently represents one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted benzofuranyl and substituted or unsubstituted dibenzofuranyl;
said L0、L1Independently represent a single bond, phenylene, naphthylene or biphenylene, and do not represent a single bond at the same time;
the dotted line indicates that two groups are either singly bonded or not bonded, but not simultaneously singly bonded;
the R is1Represented by phenylene, naphthylene or biphenylene;
the R is3Represented by a hydrogen atom, a phenyl group, a naphthyl group or a biphenyl group;
the R is2Represents one of a hydrogen atom, a deuterium atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted dibenzofuranyl group and a substituted or unsubstituted benzofuranyl group; r2Is connected with adjacent phenyl through a single bond or forms a ring;
the substituents for substitution are optionally selected from protium, deuterium, tritium, C1-10Alkyl of (C)6-30Aryl, 5 to 30 membered heteroaryl containing one or more heteroatoms.
Preferably, the arylamine carbazole compound has a structure shown in any one of general formulas (2) and (4):
Figure BDA0002868384810000022
said L is0、L1、Ar1-Ar4、R2、R3Are as defined aboveAnd (4) determining.
Preferably, the substituents for substitution are optionally selected from: deuterium, methyl, ethyl, propyl, tertiary butyl, phenyl, biphenyl, naphthyl, fluorenyl, phenanthryl, pyrenyl, benzofuranyl and dibenzofuranyl.
Preferably, the arylamine carbazole compound has a specific structure of any one of the following structures:
Figure BDA0002868384810000023
Figure BDA0002868384810000031
Figure BDA0002868384810000041
Figure BDA0002868384810000051
Figure BDA0002868384810000061
Figure BDA0002868384810000071
an organic electroluminescent device comprises an anode, a hole transmission area, a light-emitting area, an electron transmission area and a cathode from bottom to top in sequence, wherein the hole transmission area comprises the arylamine carbazole compound.
In a preferred scheme, the hole transport region sequentially comprises a hole injection layer, a hole transport layer and an electron blocking layer from bottom to top; the hole injection layer is a mixed film layer of the arylamine carbazole compound and a P-type doping material; the hole transport layer comprises the same arylamine carbazole-based compound as the hole injection layer; the light-emitting region includes a host material and a guest material, wherein the host material includes an anthracene group, and the guest material is a fluorescent material.
Preferably, the electron transport region comprises a nitrogen heterocyclic compound represented by the general formula (5):
Figure BDA0002868384810000081
in the general formula (5), Ar5、Ar6、Ar7Independently of one another, represents substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing one or more hetero atoms5-C30A heterocyclic group;
l represents substituted or unsubstituted C6-C30Arylene radical, substituted or unsubstituted C containing one or more hetero atoms5-C30A heterocyclylene group;
each of said heteroatoms is independently selected from N, O or S;
n represents 1 or 2;
X1、X2、X3independently of one another, are N or CH, and X1、X2、X3At least one of which is denoted as N.
Preferably, the nitrogen heterocyclic compound represented by the general formula (5) is represented by the general formula (5-1):
Figure BDA0002868384810000082
wherein Ar is5、Ar6、Ar7、X1、X2、X3And L are each as defined above.
Preferably, the electron transport region sequentially comprises an electron transport layer and an electron injection layer from bottom to top, wherein the electron transport layer comprises a nitrogen heterocyclic compound shown as a general formula (5), and the electron injection layer is an N-type metal material;
the specific structure of the compound represented by the general formula (5) is any one of the following structures:
Figure BDA0002868384810000083
Figure BDA0002868384810000091
a display device comprises the organic electroluminescent device.
It is also an object of the present invention to provide a full color display apparatus including three pixels of red, green and blue, the full color display apparatus including the organic electroluminescent device of the present invention.
The invention has the beneficial effects that:
the organic electroluminescent device is made by combining materials with excellent hole and electron injection/transmission performance, film stability and weather resistance, the composite efficiency of electrons and holes is improved, the exciton utilization rate is improved, and the obtained device has low driving voltage and long service life.
The arylamine carbazole compound takes an aromatic ring as a bridged arylamine carbazole type in the middle, and the arylamine and carbazole groups are connected on the aromatic ring in a dispersed manner, so that the compound disclosed by the invention has excellent hole migration capability.
In addition, the arylamine carbazole compound has higher glass transition temperature, excellent film phase stability and excellent high-temperature weather resistance because the carbazole group is a larger rigid group, so that the device cannot be aged or crystallized due to heat generated in the lighting process.
In the organic electroluminescent device of the present invention, the hole transport region includes the arylamine carbazole-based compound as described above, and since the arylamine carbazole-based compound has a strong hole injection transport capability and a suitable energy level, holes can be efficiently transported and injected into the light-emitting layer, and high-efficiency light emission at a low driving voltage of the organic electroluminescent device can be achieved.
In addition, the arylamine carbazole compound is combined with the nitrogen heterocyclic electron transport material, so that electrons and holes are in an optimal balance state, and the arylamine carbazole compound has higher efficiency and excellent service life, particularly the high-temperature service life of a device.
Drawings
Fig. 1 schematically shows a cross-sectional view of an organic light emitting diode according to an embodiment of the present invention.
1 represents an anode; 10 denotes a hole transport region, 2 denotes a hole injection layer, 3 denotes a hole transport layer, and 4 denotes an electron blocking layer; 5 denotes a light emitting region; 20 an electron transport region, 6 an electron transport layer, and 7 an electron injection layer; 8 is represented as a cathode; 9 denotes a cover layer; and 30 an organic light emitting diode.
Detailed Description
Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are merely exemplary, and the present invention is not limited thereto and is defined by the scope of the claims.
In the present invention, unless otherwise specified, all operations are carried out under ambient temperature and pressure conditions.
In the present invention, unless otherwise specified, HOMO means the highest occupied orbital of a molecule, and LUMO means the lowest unoccupied orbital of a molecule. In addition, the "difference in HOMO energy levels" and "difference in LUMO energy levels" referred to in the present specification mean a difference in absolute value of each energy value. Further, in the present invention, HOMO and LUMO energy levels are expressed in absolute values, and the comparison between the energy levels is also a comparison of the magnitude of the absolute values thereof, and those skilled in the art know that the larger the absolute value of an energy level is, the lower the energy of the energy level is.
In the present invention, when a layer or element is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or intervening layers may also be present. In addition, it will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present. Like numbers refer to like elements throughout.
In the present invention, when describing electrodes and organic electroluminescent devices, and other structures, "upper", "lower", "top", and "bottom" and the like used to indicate orientation only indicate orientation in a certain specific state, and do not mean that the related structures can exist only in the orientation; conversely, if the structure is repositioned, e.g., inverted, the orientation of the structure is changed accordingly. Specifically, in the present invention, the "bottom" side of the electrode refers to the side of the electrode that is closer to the substrate during fabrication, while the opposite side that is further from the substrate is the "top" side.
In this specification, the term "substituted" means that one or more hydrogen atoms on the designated atom or group are replaced with the designated group, provided that the designated atom's normal valency is not exceeded in the present case.
In this specification, the term "C6-C30Aryl "refers to a fully unsaturated monocyclic, polycyclic or fused polycyclic (i.e., rings that share a pair of adjacent carbon atoms) system having 6 to 30 ring carbon atoms.
In this specification, the term "C5-C30Heterocyclyl "refers to a saturated, partially saturated, or fully unsaturated cyclic group having 5 to 30 ring carbon atoms and containing at least one heteroatom selected from N, O and S, including but not limited to heteroaryl, heterocycloalkyl, fused rings, or combinations thereof. When the heterocyclyl is a fused ring, each or all of the rings of the heterocyclyl may contain at least one heteroatom.
More precisely, substituted or unsubstituted C6-C30Aryl and/or substituted or unsubstituted C5-C30The heterocyclic group means a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted m-terphenylyl group, a substituted or unsubstituted terphenylyl group
Figure BDA0002868384810000101
A group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, Substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, combinations thereof or fused rings of combinations of the foregoing groups, but not limited thereto.
In the present specification, substituted or unsubstituted C6-C30Arylene or substituted or unsubstituted C5-C30Heterocyclylene means, respectively, a substituted or unsubstituted C as defined above and having two linking groups6-C30Aryl or substituted or unsubstituted C5-C30Heterocyclic radicals, e.g. substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted tetracylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted p-terphenyleneA substituted or unsubstituted m-triphenylene group, a substituted or unsubstituted arylene group
Figure BDA0002868384810000111
A group, a substituted or unsubstituted triphenylene-ylidene group, a substituted or unsubstituted peryleneylidene group, a substituted or unsubstituted indenylidene group, a substituted or unsubstituted furyleneyl group, a substituted or unsubstituted thienylene group, a substituted or unsubstituted pyrrolylene group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolylene group, a substituted or unsubstituted oxazolylene group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolylene group, a substituted or unsubstituted thiadiazolylene group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted triazinylene group, a substituted or unsubstituted benzofuranylene group, a substituted or unsubstituted benzothienylene group, a substituted or unsubstituted benzimidazolylene group, a substituted or unsubstituted indolyl group, A substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted quinazolinylene group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted naphthyrylene group, a substituted or unsubstituted benzoxazylene group, a substituted or unsubstituted benzothiazylene group, a substituted or unsubstituted acridine group, a substituted or unsubstituted phenazinylene group, a substituted or unsubstituted phenothiazine group, a substituted or unsubstituted phenoxazylene group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted carbazolyl group, a combination thereof or a fused ring of a combination of the foregoing groups, but is not limited thereto.
In this specification, the hole characteristics refer to characteristics that are capable of supplying electrons when an electric field is applied and holes formed in the anode are easily injected into and transported in the light emitting layer due to the conductive characteristics according to the Highest Occupied Molecular Orbital (HOMO) level.
In the present specification, the electron characteristics refer to characteristics that can accept electrons when an electric field is applied and electrons formed in the cathode are easily injected into and transported in the light emitting layer due to the conductive characteristics according to the Lowest Unoccupied Molecular Orbital (LUMO) level.
Organic electroluminescent device
The present invention provides an organic electroluminescent device using an arylamine compound of the general formula (1).
In one exemplary embodiment of the present invention, an organic electroluminescent device may include an anode, a hole transport region, a light emitting region, an electron transport region, and a cathode. In addition to using the aromatic amine-based compound of the present invention in the organic electroluminescent device, the organic electroluminescent device can be prepared by conventional methods and materials for preparing organic electroluminescent devices.
The organic electroluminescent device of the present invention may be a bottom emission organic electroluminescent device, a top emission organic electroluminescent device, and a stacked organic electroluminescent device, which is not particularly limited.
In the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices may also be used. Examples thereof are transparent substrates such as glass or transparent plastic substrates; opaque substrates, such as silicon substrates; a flexible Polyimide (PI) film substrate. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, water resistance. The direction of use varies depending on the nature of the substrate. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.
Anode
Preferably, the anode may be formed on the substrate. In the present invention, the anode and the cathode are opposed to each other. The anode may be made of a conductor having a high work function to aid hole injection, and may be, for example, a metal such as nickel, platinum, copper, zinc, silver, or an alloy thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and metal oxides, such as ZnO with Al or ITO with Ag; conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1, 2-dioxy) thiophene), and polyaniline, but are not limited thereto. The thickness of the anode depends on the material used, and is generally 50-500nm, preferably 70-300nm, and more preferably 100-200nm, and ITO and Ag, which are combinations of metals and metal oxides, are preferably used in the present invention.
Cathode electrode
The cathode may be made of a conductor having a lower work function to aid electron injection, and may be, for example, a metal or alloy thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, aluminum, silver, tin, and combinations thereof; materials of multilayer structure, e.g. LiF/Al, Li2O/Al and BaF2But not limited thereto,/Ca. The thickness of the cathode depends on the material used and is generally from 10 to 50nm, preferably from 15 to 20 nm.
Light emitting area
In the present invention, the light emitting region may be disposed between the anode and the cathode, and may include at least one host material and at least one guest material. As the host material and the guest material of the light emitting region of the organic electroluminescent device of the present invention, light emitting layer materials for organic electroluminescent devices known in the art can be used. The host material may be, for example, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or 4,4' -bis (9-Carbazolyl) Biphenyl (CBP). Preferably, the host material may comprise anthracene groups. The guest material can be, for example, quinacridone, coumarin, rubrene, perylene and derivatives thereof, benzopyran derivatives, rhodamine derivatives, or aminostyrene derivatives.
In a preferred embodiment of the present invention, one or two host material compounds are contained in the light-emitting region.
In a preferred embodiment of the present invention, two host material compounds are included in the light emitting region, and the two host material compounds form an exciplex.
In a preferred embodiment of the invention, the host material of the light-emitting region used is selected from one or more of the following compounds BH-1-BH-11:
Figure BDA0002868384810000121
in the present invention, the light emitting region may include a phosphorescent or fluorescent guest material to improve the fluorescent or phosphorescent characteristics of the organic electroluminescent device. Specific examples of the phosphorescent guest material include metal complexes of iridium, platinum, and the like, and for the fluorescent guest material, those generally used in the art may be used. In a preferred embodiment of the present invention, the guest material of the light-emitting film layer used is selected from one of the following compounds BD-1 to BD-10:
Figure BDA0002868384810000122
Figure BDA0002868384810000131
in the light emitting region of the present invention, the ratio of the host material to the guest material used is 99:1 to 70:30, preferably 99:1 to 85:15 and more preferably 97:3 to 87:13 on a mass basis.
The thickness of the light emitting region may be 10 to 50nm, preferably 15 to 30nm, but the thickness is not limited to this range.
Hole transport region
In the organic electroluminescent device of the present invention, a hole transport region is provided between the anode and the light emitting region, and includes a hole injection layer, a hole transport layer, and an electron blocking layer.
Hole injection layer
The hole injection material used in the hole injection layer (also referred to as an anode interface buffer layer) is a material that can sufficiently accept holes from the anode at a low voltage, and the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is preferably a value between the work function of the anode material and the HOMO of the adjacent organic material layer. In a preferred embodiment of the present invention, the hole injection layer is a mixed film layer of a host organic material and a P-type dopant material. In order to smoothly inject holes from the anode into the organic film layer, the HOMO level of the host organic material must have a certain characteristic with the P-type dopant material, so that the generation of a charge transfer state between the host material and the dopant material is expected, and ohmic contact between the hole injection layer and the anode is realized, thereby realizing efficient injection of holes from the electrode to the hole injection layer. This feature is summarized as: the difference between the HOMO energy level of the host material and the LUMO energy level of the P-type doping material is less than or equal to 0.4 eV. Therefore, for hole-type host materials with different HOMO levels, different P-type doping materials need to be selected to match with the hole-type host materials, so that ohmic contact of an interface can be realized, and the hole injection effect is improved.
Preferably, specific examples of the host organic material include: metalloporphyrin, oligothiophene, organic materials of arylamine, hexanitrile hexaazatriphenylene, organic materials of quinacridone, organic materials of perylene, anthraquinone, polyaniline and polythiophene conductive polymers; but is not limited thereto. Preferably, the host organic material is an arylamine-based organic material.
Preferably, the P-type doping material is a compound having charge conductivity selected from the group consisting of: quinone derivatives or metal oxides such as tungsten oxide and molybdenum oxide, but not limited thereto.
In a preferred embodiment of the present invention, the P-type doping material used is selected from any one of the following compounds HI1 to HI 8:
Figure BDA0002868384810000132
in one embodiment of the invention, the ratio of host organic material to P-type dopant material used is 99:1 to 95:5, preferably 99:1 to 97:3, by mass.
In a preferred embodiment of the present invention, the hole injection layer is a mixed film layer of an arylamine-based compound and a P-type dopant material, and the arylamine-based compound is different from the arylamine-based compound of the general formula (1).
The thickness of the hole injection layer of the present invention may be 5 to 20nm, preferably 8 to 15nm, but the thickness is not limited to this range.
Hole transport layer
In the organic electroluminescent device of the present invention, the hole transport layer may be disposed on the hole injection layer. The hole transport material is suitably a material having a high hole mobility, which can accept holes from the anode or the hole injection layer and transport the holes into the light-emitting layer. Specific examples thereof include: aromatic amine-based organic materials, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like, but are not limited thereto. In a preferred embodiment, the hole transport layer comprises the same aromatic amine-based compound as the hole injection layer.
The thickness of the hole transport layer of the present invention may be 80-200nm, preferably 100-150nm, but the thickness is not limited to this range.
Electron blocking layer
In the organic electroluminescent device of the present invention, the electron blocking layer may be disposed between the hole transport layer and the light emitting layer, and particularly, contacts the light emitting layer. The electron blocking layer is provided to contact the light emitting layer, and thus, hole transfer at the interface of the light emitting layer and the hole transport layer can be precisely controlled. In one embodiment of the present invention, the electron blocking layer material is selected from carbazole-based aromatic amine derivatives. The thickness of the electron blocking layer may be 5 to 20nm, preferably 8 to 15nm, but the thickness is not limited to this range.
The invention does not deny the substrate collocation principle of the traditional hole materials, but further superposes the physical parameters screened by the traditional materials, namely, the influence effects of HOMO energy level, carrier mobility, film phase stability, heat resistance stability of the materials and the like on the hole injection efficiency of the organic electroluminescent device are acknowledged. On the basis, the material screening conditions are further increased, and the material selection accuracy for preparing the high-performance organic electroluminescent device is improved by selecting more excellent organic electroluminescent materials for matching the device.
Electron transport region
In the organic electroluminescent device of the present invention, the electron transport region is disposed between the light emitting region and the cathode, and includes an electron transport layer and an electron injection layer, but is not limited thereto.
Electron injection layer
The electron injection layer may be disposed between the electron transport layer and the cathode. The electron injection layer material is generally a material preferably having a low work function so that electrons are easily injected into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material of the organic electroluminescent device of the present invention, electron injection layer materials for organic electroluminescent devices known in the art, for example, lithium; lithium salts such as lithium 8-hydroxyquinoline, lithium fluoride, lithium carbonate or lithium azide; or cesium salts, cesium fluoride, cesium carbonate or cesium azide. The thickness of the electron injection layer of the present invention may be 0.1 to 5nm, preferably 0.5 to 3nm, and more preferably 0.8 to 1.5nm, but the thickness is not limited to this range.
Electron transport layer
The electron transport layer may be disposed over the light emitting film layer or, if present, the hole blocking layer. The electron transport layer material is a material that easily receives electrons of the cathode and transfers the received electrons to the light emitting layer. Materials with high electron mobility are preferred. As the electron transport layer of the organic electroluminescent device of the present invention, an electron transport layer material for organic electroluminescent devices known in the art, for example, in Alq, can be used3Metal complexes of hydroxyquinoline derivatives typified by BALq and LiQ, various rare earth metal complexes, triazole derivatives, triazine derivatives such as 2, 4-bis (9, 9-dimethyl-9H-fluoren-2-yl) -6- (naphthalen-2-yl) -1,3, 5-triazine (CAS No: 1459162-51-6), and 2- (4- (9, 10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d ] d]Imidazole derivatives such as imidazole (CAS number: 561064-11-7, commonly known as LG201), oxadiazole derivatives, and the like.
In a preferred organic electroluminescent device of the invention, the electron transport layer comprises a nitrogen heterocyclic derivative of the general formula (5):
Figure BDA0002868384810000141
in the general formula (5), Ar5、Ar6、Ar7Independently of one another, represents substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing one or more hetero atoms5-C30A heterocyclic group;
l represents substituted or unsubstituted C6-C30Arylene radical, substituted or unsubstituted C containing one or more hetero atoms5-C30A heterocyclylene group;
each of said heteroatoms is independently selected from N, O or S;
n represents 1 or 2;
X1、X2、X3independently of one another, are N or CH, and X1、X2、X3At least one of which is denoted as N.
Preferably, the nitrogen heterocyclic compound represented by the general formula (5) is represented by the general formula (5-1):
Figure BDA0002868384810000151
wherein Ar is5、Ar6、Ar7、X1、X2、X3And L are each as defined above.
Preferably, the electron transport region sequentially comprises an electron transport layer and an electron injection layer from bottom to top, wherein the electron transport layer comprises a nitrogen heterocyclic compound shown as a general formula (5), and the electron injection layer is an N-type metal material;
the specific structure of the compound represented by the general formula (5) is any one of the following structures:
Figure BDA0002868384810000152
Figure BDA0002868384810000161
in a more preferred embodiment of the present invention, the electron transport layer comprises any one of the compounds selected from the group consisting of:
Figure BDA0002868384810000162
the thickness of the electron transport layer of the present invention may be 10 to 80nm, preferably 20 to 60nm, and more preferably 25 to 45nm, but the thickness is not limited to this range.
Covering layer
In order to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., a CPL layer, also referred to as a capping layer) may be further added on the cathode of the device. According to the principle of optical absorption and refraction, the CPL cover layer material should have a higher refractive index as well as a better refractive index, and the absorption coefficient should be smaller as well. Any material known in the art may be used as the CPL layer material, such as Alq3, or N4, N4' -diphenyl-N4, N4' -bis (9-phenyl-3-carbazolyl) biphenyl-4, 4' -diamine. The CPL capping layer is typically 5-300nm, preferably 20-100nm and more preferably 40-80nm thick.
The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layers of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.
Hereinafter, an organic electroluminescent device according to an embodiment of the present invention is described.
In the drawings, the thickness of layers, films, substrates, regions, etc. are exaggerated for clarity. Like reference numerals refer to like elements throughout the specification. It will be understood that when an element such as a layer, film, region or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
Fig. 1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
Referring to fig. 1, an organic light emitting diode 30 according to an embodiment of the present invention includes an anode 1 and a cathode 8 facing each other, a hole transport region 10, a light emitting region 5, and an electron transport region 20 sequentially disposed between the anode 1 and the cathode 8, and a capping layer 9 disposed over the cathode, wherein the hole transport region 10 includes a hole injection layer 2, a hole transport layer 3, and an electron blocking layer 4, and the electron transport region 20 includes an electron transport layer 6 and an electron injection layer 7.
The present invention also relates to a method of preparing an organic electroluminescent device comprising sequentially laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer and a cathode, and optionally a capping layer, on a substrate. In this regard, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, LITI, or the like may be used, but are not limited thereto. In the present invention, it is preferable that the respective layers are formed by a vacuum evaporation method. The individual process conditions in the vacuum evaporation process can be routinely selected by the person skilled in the art according to the actual requirements.
In addition, the material for forming each layer described in the present invention may be used as a single layer by forming a film alone, may be used as a single layer by forming a film after mixing with another material, or may be used as a laminated structure between layers formed by forming films alone, a laminated structure between layers formed by mixing, or a laminated structure between a layer formed by forming a film alone and a layer formed by mixing.
The invention also relates to a full-color display device, in particular a flat panel display device, having three pixels of red, green and blue, comprising the organic electroluminescent device of the invention. The display device may further include at least one thin film transistor. The thin film transistor may include a gate electrode, source and drain electrodes, a gate insulating layer, and an active layer, wherein one of the source and drain electrodes may be electrically connected to an anode of the organic electroluminescent device. The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor, or an oxide semiconductor, but is not limited thereto.
Exemplary embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purposes of limitation. In some instances, features, characteristics and/or elements described in connection with a particular embodiment may be used alone or in combination with features, characteristics and/or elements described in connection with other embodiments, unless specifically indicated otherwise, as will be apparent to one of ordinary skill in the art upon submission of the present application. Accordingly, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
The following examples are intended to better illustrate the invention, but the scope of the invention is not limited thereto.
Examples
Unless otherwise indicated, various materials used in the following examples and comparative examples are commercially available or may be obtained by methods known to those skilled in the art.
Preparation of the Compound of formula (1)
Example 1: synthesis of Compound 1
Figure BDA0002868384810000171
Figure BDA0002868384810000181
Adding 0.012mol of raw material A, 0.01mol of intermediate B, 0.02mol of sodium carbonate, 100ml of toluene and 30ml of water into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 1X 10-4mol tetrakis (triphenylphosphine) palladium Pd (PPh)3)4Heating to 105 ℃, refluxing and reacting for 24 hours, sampling a sample point plate, and completely reacting at a point without the raw material B on the thin layer chromatographic plate. Naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (-0.09MPa, 85 ℃), passing through a neutral silica gel column (silica gel 100 meshes and 200 meshes, and the eluent is chloroform: n-hexane: 1:2 (volume ratio)), and obtaining the productTo intermediate M. Elemental analysis Structure (molecular formula C)24H15BrClN): test values are: c, 66.60; h, 3.45; br, 18.49; cl, 8.18; and N, 3.27. LC-MS ([ M + H)]+): found 432.20.
Adding 0.012mol of intermediate M, 0.01mol of raw material C, 0.02mol of sodium carbonate, 100ml of toluene and 30ml of water into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 1X 10-4mol tetrakis (triphenylphosphine) palladium Pd (PPh)3)4Heating to 105 ℃, refluxing and reacting for 24 hours, taking samples on a sample plate, and taking a point without the raw material C on a thin layer chromatographic plate, wherein the reaction is complete. Naturally cooling to room temperature, filtering, carrying out reduced pressure rotary evaporation on the filtrate (-0.09MPa, 85 ℃), and passing through a neutral silica gel column (silica gel 100 meshes and 200 meshes, and the eluent is chloroform: n-hexane: 1:2 (volume ratio)) to obtain an intermediate P. Elemental analysis Structure (molecular formula C)42H29ClN2): test values are: c, 84.50; h, 4.90; cl, 5.93; and N, 4.68. LC-MS ([ M + H)]+): found 597.43.
A250 ml three-necked flask was charged with 0.012mol of the raw material D, 0.01mol of the intermediate P, 0.03mol of potassium tert-butoxide, 1X 10 in a nitrogen-purged atmosphere-4mol tris (dibenzylideneacetone) dipalladium Pd2(dba)3，1×10-4mol triphenylphosphine, 150ml toluene, heated to reflux for 12 hours, and a sample of the plaque taken, indicating completion of the reaction. Naturally cooling, filtering, rotatably evaporating the filtrate, and passing through a silica gel column (silica gel 100-200 meshes, eluent: chloroform: n-hexane: 1:2 (volume ratio)) to obtain the target compound 1. Elemental analysis Structure (molecular formula C)54H39N3): test values are: c, 88.83; h, 5.40; n, 5.77. LC-MS ([ M + H)]+): found 730.45.
The following compounds (all raw materials supplied by Zhongxiao Wangrun Co., Ltd.) were prepared in the same manner as in example 1, and the synthetic raw materials were as shown in Table 1 below. The synthesis of the hole transport layer material used in the present invention refers to patent CN110577511A, and the raw materials used are all provided by zhong energy-saving ten thousand parts ltd.
For structural analysis of the compounds prepared in examples, the molecular weights were measured by LC-MS as in table 1, and 1H-NMR was measured by dissolving the prepared compound in a deuterated chloroform solvent and using a 400MHz NMR apparatus, the results of which are shown in table 2:
TABLE 1
Figure BDA0002868384810000182
Figure BDA0002868384810000191
Figure BDA0002868384810000201
TABLE 2
Figure BDA0002868384810000202
Detection method
Glass transition temperature Tg: measured by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter, Nachi company, Germany), the rate of temperature rise was 10 ℃/min.
HOMO energy level: the test was conducted in a vacuum environment by an ionization energy test system (IPS 3).
Eg energy level: based on the tangent line of the ultraviolet spectrophotometry (UV absorption) baseline of the single film of the material and the ascending side of the first absorption peak, the intersection value of the tangent line and the baseline is calculated.
Hole mobility: the material was fabricated into a single charge device and measured by space charge (induced) limited current method (SCLC).
Triplet energy level T1: the material was dissolved in toluene solution and tested by Hitachi F4600 fluorescence spectrometer.
The results of the physical property tests are shown in Table 3.
TABLE 3
Figure BDA0002868384810000211
As can be seen from the data in table 3 above, the compound of the present invention has a suitable HOMO level, a higher hole mobility, and a wider band gap (Eg), and can realize an organic electroluminescent device having high efficiency, low voltage, and long lifetime.
Preparation of organic electroluminescent device
The molecular structural formula of the materials involved in the following preparation is as follows:
Figure BDA0002868384810000212
Figure BDA0002868384810000221
comparative device example 1
The organic electroluminescent device was prepared as follows:
a) using transparent glass as a substrate, washing an anode layer (ITO (15nm)/Ag (150nm)/ITO (15nm)) on the transparent glass, respectively carrying out ultrasonic cleaning for 15 minutes by using deionized water, acetone and ethanol, and then treating for 2 minutes in a plasma cleaner;
b) on the anode layer washed, a hole transport material HT1 and a P-type dopant material HI1 were placed in two evaporation sources under a vacuum of 1.0E-5The vapor deposition rate of a compound HT1 under Pa pressure is controlled to be
Figure BDA0002868384810000222
Controlling the evaporation rate of the P-type doping material HI1 to be
Figure BDA0002868384810000223
Co-evaporating to form a hole injection layer with the thickness of 10 nm;
c) evaporating a hole transport layer on the hole injection layer in a vacuum evaporation mode, wherein the hole transport layer is made of a compound HT1 and has the thickness of 120 nm;
d) evaporating an electron blocking layer EB-1 on the hole transmission layer in a vacuum evaporation mode, wherein the thickness of the electron blocking layer EB-1 is 10 nm;
e) evaporating a luminescent layer material on the electron barrier layer in a vacuum evaporation mode, wherein a host material is BH-1, a guest material is BD-1, the mass ratio is 97:3, and the thickness is 20 nm;
f) evaporating ET1 and LiQ on the light-emitting layer in a vacuum evaporation mode, wherein the mass ratio of ET1 to LiQ is 50:50, the thickness is 30nm, and the layer serves as an electron transport layer;
g) evaporating LiF on the electron transport layer in a vacuum evaporation mode, wherein the thickness of the LiF is 1nm, and the LiF is an electron injection layer;
h) vacuum evaporating an Mg: Ag (1:9) electrode layer with the thickness of 16nm on the electron injection layer, wherein the layer is a cathode layer;
i) CPL material CPL-1 is evaporated in vacuum on the cathode layer, and the thickness is 70 nm.
Comparative device examples 2 to 3
The process of comparative device example 1 was followed except that the organic materials in steps b)/c) were respectively replaced with the organic materials shown in table 4.
Comparative device examples 4 to 6
The procedure of comparative device example 1 was followed except that the organic materials in b)/c)/f) were respectively replaced with the organic materials shown in table 4.
Device preparation examples 1 to 20
The process of comparative example 1 of the device was followed, except that the organic materials in steps b)/c) were respectively replaced with the organic materials shown in table 4.
Device production examples 21 to 40
The procedure of comparative device example 1 was followed except that the organic materials in b)/c)/f) were respectively replaced with the organic materials shown in table 4.
TABLE 4
Figure BDA0002868384810000224
Figure BDA0002868384810000231
Figure BDA0002868384810000241
Figure BDA0002868384810000251
After the OLED light-emitting device was prepared as described above, the cathode and the anode were connected by a known driving circuit, and various properties of the device were measured. The device measurement performance results of examples 1 to 40 and comparative examples 1 to 6 are shown in table 5.
TABLE 5
Figure BDA0002868384810000252
Figure BDA0002868384810000261
Note: LT95 refers to the time it takes for the device luminance to decay to 95% of the original luminance at a luminance of 1200 nits;
voltage, Current efficiency and color coordinates were tested using an IVL (Current-Voltage-Brightness) test System (Frashda scientific instruments, Suzhou) with a test current density of 10mA/cm2；
The life test system is an EAS-62C type OLED life test system of Japan scientific research corporation.
The high-temperature service life refers to the time for the brightness of the device to decay to 80% of the original brightness under the condition of 80 ℃ and the brightness of 1000 nits;
as can be seen from table 5, the results of comparative examples 1 to 3 and device examples 1 to 20, the arylamine carbazole-based compound of the present invention, which is used as a hole injection and hole transport layer material, effectively reduces the device voltage and improves the device lifetime due to its higher carrier transport rate.
It can be seen from the results of comparative examples 4 to 6 of table 5 and device examples 21 to 40 that the aromatic amine carbazole compounds of the present invention are used in combination with a specific electron transport layer material, and the efficiency and lifetime of the device are effectively improved by the matching manner.
The compound contains one or more carbazole groups, can effectively improve the glass transition temperature of the material, and has high heat-resistant stability, so that the compound has excellent film phase stability and evaporation stability, the interface stability of a device under a high-temperature condition is effectively improved, and the device has excellent high-temperature service life.
While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the described embodiments. But, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. The foregoing embodiments are therefore to be considered in all respects illustrative and not restrictive.

Claims (10)

1. An arylamine carbazole compound is characterized in that the structure of the compound is shown as a general formula (1):
Figure FDA0002868384800000011
ar is1-Ar4Each independently represents one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted benzofuranyl and substituted or unsubstituted dibenzofuranyl;
said L0、L1Independently represent a single bond, phenylene, naphthylene or biphenylene, and do not represent a single bond at the same time;
the dotted line indicates that two groups are either singly bonded or not bonded, but not simultaneously singly bonded;
the R is1Represented by phenylene, naphthylene or biphenyl;
the R is3Represented by a hydrogen atom, a phenyl group, a naphthyl group or a biphenyl group;
the R is2Represents one of a hydrogen atom, a deuterium atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted benzofuranyl group and a substituted or unsubstituted dibenzofuranyl group; r is2Is connected with adjacent phenyl through a single bond or a ring-merging form;
the substituents for substitution are optionally selected from protium, deuterium, tritium, C1-10Alkyl of (C)6-C30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms.
2. The arylamine carbazole-based compound according to claim 1, wherein the structure of the arylamine carbazole-based compound is represented by any one of general formula (2) to general formula (4):
Figure FDA0002868384800000012
said L0、L1、Ar1-Ar4、R2、R3Is as defined in claim 1.
3. The arylamine carbazole compounds of claim 1, wherein the substituent for substitution is optionally selected from: deuterium, methyl, ethyl, propyl, tert-butyl, phenyl, biphenyl, naphthyl, fluorenyl, phenanthryl, pyrenyl, benzofuranyl and dibenzofuranyl.
4. The aromatic amine carbazole-based compound according to claim 1, wherein the specific structure of the aromatic amine carbazole-based compound is any one of the following structures:
Figure FDA0002868384800000013
Figure FDA0002868384800000021
Figure FDA0002868384800000031
Figure FDA0002868384800000041
Figure FDA0002868384800000051
Figure FDA0002868384800000061
Figure FDA0002868384800000071
5. an organic electroluminescent device, which sequentially comprises an anode, a hole transport region, a luminescent region, an electron transport region and a cathode from bottom to top, wherein the hole transport region comprises the arylamine carbazole-based compound as claimed in any one of claims 1 to 4.
6. The organic electroluminescent device according to claim 5, wherein the hole transport region comprises a hole injection layer, a hole transport layer and an electron blocking layer in sequence from bottom to top; the hole injection layer is a mixed film layer of the arylamine carbazole compound and the P-type doping material according to any one of claims 1 to 4; the hole transport layer comprises the same arylamine carbazole-based compound as the hole injection layer; the light-emitting region includes a host material and a guest material, wherein the host material includes an anthracene group, and the guest material is a fluorescent material.
7. The organic electroluminescent device according to claim 5, wherein the electron transport region comprises a nitrogen heterocyclic compound represented by general formula (5):
Figure FDA0002868384800000072
in the general formula (5), Ar5、Ar6、Ar7Independently of one another, represents substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C containing one or more hetero atoms5-C30A heterocyclic group;
l represents substituted or unsubstituted C6-C30Arylene radical, substituted or unsubstituted C containing one or more hetero atoms5-C30A heterocyclylene group;
each of said heteroatoms is independently selected from N, O or S;
n represents 1 or 2;
X1、X2、X3independently of one another, are N or CH, and X1、X2、X3At least one of which is denoted as N.
8. The organic electroluminescent device according to claim 7, wherein the nitrogen heterocyclic compound represented by the general formula (5) is represented by a general formula (5-1):
Figure FDA0002868384800000073
wherein Ar is5、Ar6、Ar7、X1、X2、X3And L are each as defined in claim 7.
9. The organic electroluminescent device according to claim 7, wherein the electron transport region comprises an electron transport layer and an electron injection layer in this order from bottom to top, wherein the electron transport layer comprises a nitrogen heterocyclic compound represented by general formula (5), and the electron injection layer is an N-type metal material;
the specific structure of the compound represented by the general formula (5) is any one of the following structures:
Figure FDA0002868384800000074
Figure FDA0002868384800000081
10. a display device comprising the organic electroluminescent element as claimed in any one of claims 5 to 9.
CN202011598579.8A 2020-12-29 2020-12-29 Arylamine carbazole compound and organic electroluminescent device containing same Withdrawn CN114685356A (en)

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